Alfred eisenstein



Patented Dec. 8, 1925.

UNITED STATES PATENT OFFICE.

ALFRED EISENSTEIN, OF LEITMERITZ, CZECI-IOSLO VAKIA, ASSIGNOR OF ONEQHA LF TO THE FIRM GEOBG SCHICHT, A.-G.,OF AUSSIG, CZECHOSLOV AKIA.

rnoonss non OXIDIZING oILs.

No Drawing.

To all 20710212 e't may concern Be it known that I. Anrnnn EISENSTEIX, an Austrian citizen, residing at \Vallstrasse, Leitmeritz, Czechoslovakia, have invented certain new and useful Improvements in Processes for oxidizing Oils, for which I have made application for patent in Czechoslovakia on April 3, 1919, and on April 16, 1919; in Germany on April 2 t, 1920; in Spain on April 12, 1920; in Holland on April 3, 1920, and on April 7 1920; in Sweden on April 7, 1920; in Belgium on July 9, 1920; in Italy on July 7 1920; and in France on June 30, 1920, and of 'which the following is a specification.

Hitherto widely varying processes have been used for the oxidation of oils dependent upon the initial product employed and the final purposes in View, and they may be divided up into two groups. In the first group air is allowed to act at a moderate temperature upon a thin film of oil, and in the second group the air is driven through a large mass of oil at a higher temperature.

As typical of the first group I may mention the \Valton process for the manufacture of linoxyn (see the specifications of British .Letters Patent No. 209 of 1860 and 2845 of 1872 and German Patent No. 80,584) in which the oil runs downward over a piece of fabric, the thin film which remains adherent thereto being subjected to the action of air. A defect of this method is that the contact surface is relatively small, it corresponds to the dimensions of the fabric, and the duration of the operation consequently extends over a period of from four to six months. A modification of the Valton process aims at increasing the contact surface by allowing the oil to fall through the air in the form of rain. \Vith this method the time of contact is too short, if only one shower be used, and the consequently necessary repeated raising of the masses of oil requires a large expenditure of power and also interrupts the oxidation so that the saving of time effected is of no practical value.

Now when, in connectionwith the action of a gas upon a liquid, it is a question of obtaining a large contact surface, recourse is generally had to the step of allowing the liquid to flow over substances such as pumice-stone, fragments of earthenware,

Application filed January 18, 1921. Serial No. 438,243.

glass beads and the like. This method however is based upon the assumption that an easily fluent or readily soluble product results from the liquid through the influence of the gas, so that by means of one or the other of these properties the separation can be effected from the reaction product and from the distributive medium. Upon the oxidation of oils, however, bodies are produced which even at high temperatures. are solid or very viscid, whilst many of them are insoluble in technical solvents.

Hertkorn has also proposed an oxidation method (German Patents Nos. 100917 and 109583) according to which no subsequent. separation is necessary. He mixes the oil with those loose specifically light, powdery or fibrous materials (cork, sawdust, animal, vegetable and mineral fibres) which are required to be present in the final product (linoleum) and exposes the mixture to a current of air in a mixing apparatus. This process is attended by the drawback that the product of oxidation always contains extraneous substances and, consequently only answers for the one purpose according to thesubstance added whilst, furthermore. any desired quantities cannot be oxidized since the proportions of the mixture are bound by the composition of the finished product.

According to a process for the production 7 not be regulated and must, furthermore,

be interrupted at a period of time when the oil is still liquid, so that it excludes the production of highly or perfectly oxidated oils.

According to the second group mentioned air is blown through the hot oil. In this way, however, products are obtained, which,

neither physically nor chemically, are identical with the oxidation products of the first group, and they are only partly. applicable for the same purposes. Owing to the necessarily high temperature employed and to the small contact surfaces there is produced a weakly oxidized pie-eminently polymerized product. Thus, for instance,

the linoxyn made by the Parnacott rocess (British'Letters Patent No. 2057 0 1.871,) is, in comparison with that v according to Walton, of dark colour, empyreumatic odour and of a low melting point and acts 'in an entirely different manner therefrom in the presence of solvents.

N ow I have-found a new process, or rather an entirely novel working principle which i is admirably suitable for the oxidation of animal and-vegetable oils and possesses none of the drawbacks connected with the old processes. For instance there is obtained upon the oxidation of linseed oila linoxyn of the same quality as Waltons product in a period of time which is shorter than that I required by the Parnacott process. Also the oxidation can be regulated and the final product is free from foreign matter and is thus applicable for various purposes (linoleum, lincrusta,'oil-cloth, leather substitute,

rubber substitutes, etc.). The same advan-.

tages are obtained by the oxidation of other oils which, like rapeseed oil for instance, have hitherto only been blown. V

The oxidation of fatty oils according to this new process consists substantially in the fact that the vegetable or animal oil to be oxidized is finely distributed in or over a material the special characterjof which, upon completion of the oxidation, allows the separation to be effected by melting or dissolving said material or substance itself and not the reactive product.

As dispersive or diluent means sub- "stances can be used in which the oil will dissolve, such for instance as Chinese tal-' low, pressed tallow, highly pressed or hydrogenated oil, wax, parafiine, ceresine, =ste'arine, colophony and the like. However, substances in which the fatty oils will not dissolve can also be used as a distributing dized, although such substances are usually.

afterwards added to the finished product of oxidation, such as colophony, kauri 'gum and the like when manufacturing linoleum/ Linoleum cement is then obtained direct.

. An essential advantage of the process is, .that the reaction can be carried out at-a low temperature and without the supply of any heat, yet, owing to the extraordinary acceleration, the reaction takes place very quickly.-

The natural, neutralized, steamed or blown. oil, which has been obtained by a combination of the three last named treatments, is combined by melting it up or mixing it with "the substance serving as a distributing medium, eithe rwith or without the addition of a dryer or siccative. In the latter case the distributor already possesses the finely distributed, for in stance powdery, form in the first wnamed case the mixture is first of all given this character after setting, as for instance by crushing, scraping, stripping, spraying, etc. This crushing or disintegration can be dis pensed with if, as a distributive medium,

a substance 'be used which possesses the property of setting in a porous form. This porous form can also be obtained by passing air in the manner known into the solution of the oil to be oxidized, in a. substance which does not possess this property, during the process of. congelation or ,setting The mixing proportions of oil and of dispersive or diluent medium canbe varied within broad limits. It depends upon nature of the oil and of the distributing medium, and upon the constructional form as regards. apparatus and temperature.

The .mixture is exposed to atmospheric influence. This can be effected either upon hurdles, in connection with which active shovellmg 15 of great assistance or else" in rotary or otherwise movable closed apparatus, through which a current of air passes with a view to the renewal of the air and to the carrying away and recovery of the volatile products of reaction.

As soon as the oxidation is completed the products of oxidation are separated from.-the, distributing medium by melting.

and subsequent pressing operations, and by centrifugalization, if the oxidation product in the distributing medium is insoluble, as for instance linoxyn in hardened oil, or by dissolving" the distributing medium in a medium'in which the distributor is soluble, but not the oxidation product.

It is possible also to use the oxidized oil itself as the (dispersive medium. The oils oxidized according to the process referred to (linoxyn tugoxine etc.) are most sultable for this purpose because these products may be obtained in a spongy crumblike form and do not require first of all to be fractionated. They may be simply mixed or impregnated with the oil, which is to be oxidized and the mixture then exposed to the influence of oxygen, air," or other gas containing oxygen. The proportion of the mixture may be varied up to the maximum quantity of oil that the oxidized product Will absorb. The oxidation may .be carried out at the usual temperature or at a higher temperature, for example 40-60 centigrade, or even higher. Of course it is not necessary to separate the oxidized product from the distributive medium as both substances are identical. The yield is that which is theoretically calculated, for example, 100 parts of granulated linoxyn mixed with 50 parts of linseed oil varnish produce whenthe oxidation is finished not less than 158.8 parts of linoxyn.

The following examples will serve to illustrate the method of carrying out this invention, but it is tobe understood that the invention is not restricted thereto.

1st crample.750 kilogrammes complete-- mixed together with 3 per cent of its own weight of manganese resinate in 250 kilogrammes linseed 011. After this mixture has set it is disintegrated in acentrifugal machine, the powdery substance is spread upon hurdles and then mechanically turned over from time to time. This is continued, until the melting of asample shows that the linseed oil has been converted into the desired solid state. The mass is now melted. the linoxyn arising from the linseed oil, by drawing off the melted sunflower oil, is first of all freed from the main quantity thereof by pressing the residue. In this way the linoxyn is obtained in the form of slabs.

212d e.I.u'mzp.7e.-G0O kilogrammes perfectly hardened sunflower oil are melted and mixed together with 400 kilogrammes lin seed oil to which is added 3 per cent of its weight in lead resinate. After setting the mixture is formed into strips or ribbons by means of a Suitablei-milling machine. The subsequent treatment is similar to that given in the first example.

3rd e-..rampZe.-O kilogrammes paraflin are mixed in a molten condition with 300 kilogrammes linseed oil and the mixture is used in the form of a fine spray by means of nozzles. \Vhen the oxidation is completed then the linoxyn is separated from the paraf- [in according to the two foregoing examles. I

.lfh e.r(mz-pZe.800- kilogrammes finely powdered kitchen salt are thoroughly mixed together with 100 kilogrammes linseed oil, the mixture is passed into a rotary drum, which can be heated up to 100 (1, in which it is exposed to the oxidizing action of a currentof air which is afterwards passed through soda lye by means of which the carbonic acid, acetic acid. formic acid, etc. are. bound.

pleted the drum is emptied and the mixture As soon as the oxidation is comis lixiviated with water, the linoxyn is obtained in a flocculent form.

5th e:ca221-p?e.7 00 kg. parafiine are mixed in the molten state with 300 kg. train oil;

the mixture is passed through'nozzles as a fine spray and thereby converted into powdery form in which the oxidationo'ccurs as in the preceding examples.

6th er(. mp.7e.650 killogrammes sulphate of soda are mixed, according to example i, with 350 kilogrammes trainoil and then treated as set forth in said example. Then the oxidation is completed the salt is dissolved with water. The oxidized oil can now also be extracted'with a suitable solvent medium.

7H2 6:00.122 pZe.S0O kilogrammes perfectly hardened sunflower oil are melted and mixed together with 200 kilogrammes linseed oil to which there is added 3 per cent of its weight in manganese iesinate. Whilst setting air is driven into this mixture by the aid of a mixing machine. As soon as the mass has ecquired a pulp like orpasty consistency and the air can no longer escape it is poured off into moulds but is not subjected to any further disintegration. After setting the cakes or slabs thus obtained. are allowed to stand for 24: hours whereupon they are again melted, the linoxyn originating from the linseed oil is first of all, by drawing off the melted sunflower oil, freed .from the main quantity thereof by subjecting the residue to pressure.

8th ezrample.900 kg. of linoxyn are comminuted and are mixed with 100 kg. linseed oil in a rotary drum, which can be heated to 120 C, in which drum the mixture is exposed to the oxidizing action of a current of air. As soon as the linseed oil is oxidized and thereby has been converted into linoxyn. a portion of the final product is removed from the drum for further treatment, while the rest isleft in the drum for the next oxidizing operation. lVhat I claim and desire to secure by Letters Patent of the United States is 2-- 1.. Process of oxidizing oils with unsaturated bonds which consists in mixing the oil with an auxiliary substance capable of congealing at the oxidationtemperature. exposing the mixture to the action of an oxidizing agent, and then separating the oxidized product from the said auxiliary substance by liouefying the latter.

2. Process of oxidizing oils with unsaturated bonds which consists in mixing the oil with a distributing medium, adding a' re action accelerator, exposing the mixture to the action of an oxidizing gas, liouefying the said distributing medium. and finally separating the latter from the oxidized product.

3. Process of oxidizing oils with unsaturated bonds which consists in mixing the oil with a distributing substance capable of accelerating the oxidation. exposing the mixture to the action of an oxygen containing gas. and finally separating the oxidized v the action of an oxygen containing gas, and

finally separating the said congealed porous substance from the oxidized product.

5. In the process of oxidizing .oil, the step of adding the oil to be oxidized'to the previously oxidized oil being in a spongy crumb-like form which oxidized oil is insoluble in the oil to be oxidized at normal temperatures, thus presenting a large surface to the oil to be oxidized,- while maintaini mg the mass in a dismtegrated state, and exposing the mixture to the action of an oxidizin agent at a temperature of 4060 C. 6. ,n the process of oxidizing oil the step of coating the particles of a previously oxidized crumblike' oil with the oil to be oxidized, said oxidized oil being insoluble in the oil to be oxidized at normal temperatures, thus presenting-a large surface to the oil to be oxidized, and exposing the mixture to the action of an oxygencontaining gas.

In testimony whereof I affix my signature.

' DR. ALFRED iaIsENsTEIN. 

